EP0039653B1 - Préparation de l'acide acétique par carbonylation - Google Patents

Préparation de l'acide acétique par carbonylation Download PDF

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Publication number
EP0039653B1
EP0039653B1 EP81420067A EP81420067A EP0039653B1 EP 0039653 B1 EP0039653 B1 EP 0039653B1 EP 81420067 A EP81420067 A EP 81420067A EP 81420067 A EP81420067 A EP 81420067A EP 0039653 B1 EP0039653 B1 EP 0039653B1
Authority
EP
European Patent Office
Prior art keywords
process according
alkyl
nickel
formula
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81420067A
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German (de)
English (en)
French (fr)
Other versions
EP0039653A1 (fr
Inventor
Jean Gauthier-Lafaye
Robert Perron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhone Poulenc Chimie de Base SA
Original Assignee
Rhone Poulenc Chimie de Base SA
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Filing date
Publication date
Application filed by Rhone Poulenc Chimie de Base SA filed Critical Rhone Poulenc Chimie de Base SA
Priority to AT81420067T priority Critical patent/ATE3969T1/de
Publication of EP0039653A1 publication Critical patent/EP0039653A1/fr
Application granted granted Critical
Publication of EP0039653B1 publication Critical patent/EP0039653B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols

Definitions

  • the present invention relates to a process for the preparation of acetic acid, by carbonylation of methanol.
  • acetic acid can be produced by carbonylation of methanol, under relatively severe pressure conditions, in the presence of nickel and a free or combined halogen.
  • the subject of the present invention is therefore an improved process for the carbonation of methanol in the liquid phase at a temperature above 120 ° C. and under a total pressure below 200 bars in the presence of an effective amount of nickel, of a halide of alkyl or acyl, at least one lanthanide salt and an initially charged carboxylic acid.
  • the research which led to the present invention made it possible to bring out the surprising behavior of the lanthanide salts as cocatalysts of the carbonylation reaction of an alcohol, in the liquid phase and under a total pressure of less than 200 bars.
  • the Applicant has in fact found that the salts and other derivatives of many metals (including carbonyl metals) do not allow carbon monoxide to react under the above conditions with an alcohol, in a carboxylic acid, in the presence of nickel and a halogenated promoter.
  • the process according to the present invention is carried out in the liquid phase in the presence of a carboxylic acid, of formula R'-COOH, initially charged, in which R 'represents a linear, branched or cyclic alkyl radical containing from 1 to 6 carbon atoms or a radical -C n H 2n - in which n is an integer between 1 and 6 (1 sns6).
  • R ' represents a linear, branched or cyclic alkyl radical containing from 1 to 6 carbon atoms or a radical -C n H 2n - in which n is an integer between 1 and 6 (1 sns6).
  • the carboxylic acid which plays a sort of solvent role is not necessarily the carboxylic acid produced by the carbonylation reaction.
  • the carboxylic acid used as solvent is that produced by the reaction.
  • the use of a carboxylic acid heavier than the acid produced as solvent can facilitate separation operations.
  • the carboxylic acid R'COOH represents at least 10% by volume of the initial reaction medium. Preferably, it represents at least 20% by volume of the reaction medium. It can represent a significant part of the reaction medium, in particular in the case of an operation carried out continuously by injecting the alcohol into the carbonylation reactor.
  • the method according to the invention requires the presence of an effective amount of nickel.
  • Any source of nickel can be used in the context of the present process.
  • Nickel can be introduced in its metallic form (RANEY nickel, for example) or in any other convenient form.
  • nickel compounds capable of being used for the implementation of the present process there may be mentioned: carbonate, oxide, hydroxide, halides, in particular iodide, carboxylates, especially acetate, nickel.
  • Nickel carbonyl is also suitable.
  • RANEY nickel, nickel iodide, nickel acetate and nickel carbonyl are preferably used.
  • the amount of nickel is not critical.
  • the nickel content which influences the reaction rate is determined as a function of the reaction rate which is considered suitable. In general, an amount between 5 and 2000 milligrams of nickel per liter of solution leads to satisfactory results.
  • the operation is preferably carried out with a content of between 20 and 1000 milligram atoms of nickel per liter.
  • the process according to the present invention also requires the presence of at least one alkyl or acyl halide.
  • These halides have the formula respectively in which X represents a chlorine, bromine atom or, preferably, an iodine atom, and R 2 has the meaning given for R ', R 2 and R' can be identical or different.
  • the alkyl halide which can be used initially in the reaction medium is capable of being formed in situ from halogenated derivatives such as C1 21 Br 2 , 1 2 , HCI, HBr, HI, NiBr 2 and Nile 2 , and alcohol (starting material).
  • part or all of the alkyl halide necessary for carrying out the present process can be formed from its "precursors" defined above.
  • the halogenated derivative when chosen from nickel compounds, it can be considered as a precursor not only of the alkyl halide but also as a precursor of the metal catalyst. In this particular case, it is preferable to additionally charge, initially, an alkyl or acyl halide and / or a precursor distinct from the nickel halides in question.
  • lower alkyl iodides having from 1 to 4 carbon atoms constitute a preferred class of alkyl halides.
  • Methyl iodide is particularly suitable for carrying out the process according to the invention.
  • a concentration of alkyl or acyl halide of at least 0.5 mol per liter of reaction medium is generally required.
  • increasing the concentration of alkyl or acyl halide has a favorable effect on the reaction rate, it is preferable not to exceed a concentration of the order of 8 moles per liter.
  • a concentration of alkyl or acyl halide of between 0.8 and 6 moles / liter and preferably between 1.5 and 5 moles / liter leads to satisfactory results.
  • One of the essential characteristics of the present invention resides in the use of at least one lanthanide salt, that is to say of at least one compound chosen from halides, hydroxides, oxychlorides, carbonates, oxalates and carboxylates of elements whose atomic number is between 57 inclusive and 71 inclusive;
  • the carboxylate anions can be represented by the formula R 3 COO-, in which R 3 has the meaning given for R 1 , R 3 and R ′ which may be identical or different;
  • the lanthanide salts can be in hydrated form.
  • the lanthanum, cerium and neodymium salts are particularly suitable for the implementation of the present process.
  • the precise nature of the anionic part of the lanthanide salt does not appear to be a fundamental parameter of the present process.
  • the lanthanide carboxylates and more particularly the acetates are of convenient use and as such may be recommended for the implementation of the present invention.
  • Lanthanum, cerium and neodymium acetates are well suited.
  • the atomic ratio M / Ni, M denoting a lanthanide is between 0.1 and 200 although, lower or higher ratios can be chosen.
  • This ratio is advantageously fixed at a value between 0.5 and 100, and preferably between 1 and 50.
  • a reaction temperature of at least 120 ° C is generally required to obtain a satisfactory reaction rate.
  • a temperature range between 160 and 220 ° C is advantageous.
  • Alcohols and carboxylic acids of technical quality can be used, optionally containing up to 20% by volume of water.
  • all or part of the alcohol can be used in the reaction in the form of an ester of an acid R'COOH R 'having the meaning given previously. In this case, it will also be necessary to initially initiate water in an amount at least equal to the amount theoretically necessary to hydrolyze the ester loaded initially.
  • the carbonylation process according to the present invention is carried out in the liquid phase under a pressure greater than atmospheric pressure, the pressure however being less than 200 bars. It is more particularly recommended to operate under a partial pressure of carbon monoxide of between 10 and 100 bars. Carbon monoxide is preferably used in essentially pure form, as it is commercially available. However, the presence of impurities such as, for example carbon dioxide, oxygen, methane and nitrogen is not harmful. The presence of hydrogen is not harmful, even in relatively large proportions.
  • reaction mixture is separated into its various constituents by any suitable means, for example by distillation.
  • the process according to the invention is particularly suitable for the preparation of acetic acid by carbonylation of methanol, in particular in acetic acid.
  • the examples below illustrate the present invention without, however, limiting its field or spirit.
  • a pressure of 40 bars of carbon monoxide is established.
  • the agitation by a back and forth system is started and the autoclave is brought to 180 ° C, in about 20 minutes, by means of a ring oven.
  • the pressure in the autoclave is then 66 bars; it is then maintained equal to 70 bars by refills of pure CO.
  • the productivity (Pr) of the acetic acid reaction was therefore 300 grams per hour per liter (g / hx1).
  • Example 1 was reproduced above, but using various cocatalysts. The specific conditions as well as the results obtained are shown in Table I below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
EP81420067A 1980-05-06 1981-05-04 Préparation de l'acide acétique par carbonylation Expired EP0039653B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81420067T ATE3969T1 (de) 1980-05-06 1981-05-04 Verfahren zur herstellung von essigsaeure durch carbonylierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8010541 1980-05-06
FR8010541A FR2484404A1 (fr) 1980-05-06 1980-05-06 Preparation d'acides carboxyliques par carbonylation

Publications (2)

Publication Number Publication Date
EP0039653A1 EP0039653A1 (fr) 1981-11-11
EP0039653B1 true EP0039653B1 (fr) 1983-06-29

Family

ID=9241841

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81420067A Expired EP0039653B1 (fr) 1980-05-06 1981-05-04 Préparation de l'acide acétique par carbonylation

Country Status (9)

Country Link
US (1) US4426537A (pt)
EP (1) EP0039653B1 (pt)
JP (1) JPS572236A (pt)
AT (1) ATE3969T1 (pt)
BR (1) BR8102749A (pt)
CA (1) CA1167062A (pt)
DE (1) DE3160521D1 (pt)
ES (1) ES501890A0 (pt)
FR (1) FR2484404A1 (pt)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8807284D0 (en) * 1988-03-26 1988-04-27 Bp Chem Int Ltd Chemical process
JP2689517B2 (ja) * 1988-09-22 1997-12-10 三菱瓦斯化学株式会社 α−（４−イソブチルフェニル）プロピオン酸の製造法
US6137000A (en) * 1999-02-16 2000-10-24 Eastman Chemical Company Method for carbonylation of lower aliphatic alcohols using a supported iridium and lanthanide series catalyst
US8835681B2 (en) * 2010-06-14 2014-09-16 Celanese International Corporation Methanol carbonylation process with rhodium catalyst and a lanthanide metal co-catalyst

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2068265A (en) 1932-01-06 1937-01-19 Du Pont Preparation of carboxylic acids
US2135451A (en) 1935-07-13 1938-11-01 Du Pont Organic acid synthesis
US2650245A (en) 1949-04-08 1953-08-25 British Celanese Synthesis of acetic acid from co and methanol
US4133963A (en) 1975-11-19 1979-01-09 Eastman Kodak Company Process for the production of carboxylic acids
US4356320A (en) 1976-11-08 1982-10-26 The Halcon Sd Group, Inc. Preparation of carboxylic acids
DE2846148A1 (de) * 1978-10-24 1980-05-08 Hoechst Ag Verfahren zur herstellung von ethanol aus synthesegas

Also Published As

Publication number Publication date
JPS572236A (en) 1982-01-07
FR2484404A1 (fr) 1981-12-18
ATE3969T1 (de) 1983-07-15
ES8202779A1 (es) 1982-03-01
DE3160521D1 (en) 1983-08-04
BR8102749A (pt) 1982-01-26
CA1167062A (fr) 1984-05-08
FR2484404B1 (pt) 1982-07-02
JPS5737577B2 (pt) 1982-08-10
US4426537A (en) 1984-01-17
EP0039653A1 (fr) 1981-11-11
ES501890A0 (es) 1982-03-01

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